JPS6051491B2 - Production method and adsorption treatment method for phenol/aldehyde/chelate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing and adsorbing phenol and aldehyde chelate resins.

Various research reports have been made on chelate resins in which ligands capable of forming complexes with heavy metal ions are introduced into polymer compounds. (Tau・
Chemical Co., Ltd.), Diaion CR-10, 20 (Kiyoshi Kasei Co., Ltd.) and Uniselect UR-10, 2O, 30
(manufactured by Unitika) have been commercialized.

However, these resins have extremely poor selectivity for adsorbed heavy metal ions, and in particular have problems with selective trapping performance for uranium. Furthermore, many studies have been conducted on chelate resins having phosphonic acid groups, and their selective adsorption ability for certain metals, such as uranium, has been reported.
Chelate resins that simply have phosphonic acid groups are rarely commercialized due to the complicated manufacturing process, high costs, expensive raw materials, and low resin strength. However, the selective adsorption ability for uranium was not sufficient, and it was almost impossible to apply it to the separation and recovery of uranium from seawater, crude phosphoric acid for fertilizer, etc. 1st side, No, Anal-Khin 2 o'clock, 1284
Page, 1974, describes a method for producing styrenic resins of the iminodiethylene phosphonic acid type.

However, this method requires long and complicated steps to produce iminodiethylenephosphonic acid, and the cost of raw materials is high, so in reality, it cannot be used industrially. In view of these circumstances, the present inventors conducted intensive research with the aim of easily and inexpensively producing a chelate resin that exhibits excellent selective adsorption ability, especially for uranium. We have discovered that all of the above objectives can be achieved by converting a compound into a resin by introducing phosphonic acid into the amino group of the compound.
The invention has been completed.

That is, in the present invention, a compound having a phenolic hydroxyl group and a primary and/or secondary alkylamino group in the same molecule is reacted with phosphorous acid and an aldehyde in the presence of a mineral acid to convert the alkylamino group into a hydrogen atom. A phenol having a crosslinked structure is obtained by obtaining a reaction product in which part or all of the phenol is substituted with methylene phosphonic acid, and then subjecting the obtained reaction product to a condensation reaction with a phenol and an aldehyde.
Some of the phenols constituting the aldehyde-based chelate resin have a benzene nucleus in which part or all of the hydrogen atoms directly connected to the nitrogen atoms of the primary and/or secondary alkylamino groups are replaced with methylene phosphonic acid groups. The present invention is a method for producing a phenol aldehyde-based chelate resin, which is a type of phenol, and an adsorption treatment method characterized by selectively adsorbing heavy metal ions in an aqueous solution using the chelate resin.

In the present invention, it is preferable that a portion of the phenols constituting the phenol aldehyde resin is, for example, about 16 to 91 mol %, calculated from the charge amount shown below.

A compound having a phenolic hydroxyl group and a primary and/or secondary alkylamino group in the same molecule used in the present invention (hereinafter referred to as a phenol compound having an amino group).

) has a phenolic hydroxyl group and a primary and/or
Or if it has a secondary alkylamino group,
Any compound may be used. Among such compounds, preferred compounds include those of general formula (1) such as salicylamine, tyramine, and p-hydroxybenzylamine.
(n represents an integer from 1 to 20.

) Compounds having a phenolic hydroxyl group and a primary alkylamino group in the same molecule, tyrosine, o-hydroxyphenylglycine, p-hydroxyphenylglycine, etc. with the general formula (■) (n is an integer from 1 to 20) represent.

) Compounds having a phenolic hydroxyl group and a primary alkylamino group in the same molecule, 2,4-dihydroxybenzylamine, 4,4''-dihydroxybenzylamine, etc. with the general formula (■) (N, m are Represents an integer from 1 to 20.

) has a phenolic hydroxyl group and a secondary alkylamino group in the same molecule, such as ammoniaresol obtained by reacting ammonia with a phenol and an aldehyde. A compound having a secondary alkylamino group, a polyethylene◆phenol◆formalin condensate obtained by reacting polyethyleneimine with a phenol and an aldehyde, has a phenolic hydroxyl group and primary and secondary alkylamino groups in the same molecule. Examples include compounds that have

Further, the following general formula (■) (N and m represent positive numbers from 1 to 20).

), the hydrogen of the benzene nucleus is an alkylamino group with 2
It may also be a compound substituted with 2 or more.

Examples of the phenols used in the present invention include 1-phenol, 20-cresol, m-cresol,
p-cresol, 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, α-naphthol, β
- Alkyl-substituted monohydric phenols such as naphthol, o-ethylphenol, m-ethylphenol, p-ethylphenol, dihydric phenols such as 3-catechol, resorcinol, bisphenol A, and trihydric phenols such as 4-pyrogallol and chloroglucin. .

These can be used alone or in combination. Examples of the aldehydes used in the present invention include aliphatic saturated aldehydes such as formaldehyde, acetaldehyde, and propionaldehyde, aromatic aldehydes such as benzaldehyde and salicylaldehyde, heterocyclic aldehydes such as furfural, paraformaldehyde, and hexamethylene. Examples include formaldehyde derivatives such as tetramine.

These can be used alone or in combination. The chelate resin of the present invention can be produced, for example, by the following method. First, in the first step, a phenolic compound having an amino group is reacted with phosphorous acid and an aldehyde at 80 to 120°C in the presence of a mineral acid such as hydrochloric acid or sulfuric acid to convert the hydrogen atom of the alkylamino group. A part or all of it is substituted with a methylene phosphonic acid group. Then the second
As a step, the reaction product obtained in the first step is called an iminomethylenephosphonic acid derivative. ), phenols, and aldehydes in the presence of a mineral acid or an alkali compound such as sodium hydroxide, potassium hydroxide, or ammonia at 30 to 200°C, preferably 50 to 130°C.
to perform a condensation reaction. In this case, the iminomethylenephosphonic acid derivative obtained in the first step may be isolated and the condensation reaction may be carried out, or the condensation reaction may be carried out directly without isolation. In addition, bead-shaped resin can be obtained by performing the condensation reaction in the second stage by adding a solvent substantially insoluble in water to form a suspension system. As the amount of preparation,
The molar ratio of the phenol compound having an amino group, phosphorous acid, and aldehydes in the first stage is 1:0.9n to 1.5.
r1:0.9n-nod, preferably 1:1n-1.3n:
1.1 to 1.5n (n represents the number of hydrogen atoms in the alkylamino group), and the aldehydes in the second stage are:
0.5 to 1 mole, preferably 5 to 8 times the mole of the phenol compound having an amino group, and 0.1 to 5 times the mole of the phenol compound having an amino group, preferably 1 to 2.5 times the mole of the phenol. It is. As the phosphorous acid used in the first step, a compound that generates phosphorous acid by reaction (eg, triethyl phosphorite, dibutyl phosphorite) may be used. In addition, the substantially water-insoluble solvent used in the above-mentioned condensation reaction includes, for example, saturated or unsaturated aliphatic hydrocarbons such as hexane, octane, and octene; alicyclic hydrocarbons such as cyclohexane and delicalin; Examples include aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as dichloroethane and dichlorobenzene in which some or all of the hydrogen atoms of these hydrocarbons are replaced with chlorine, fluorine, or bromine. Alternatively, they can be used in combination. In addition to being used alone, the resin of the present invention may be supported on a porous carrier such as activated carbon or zeolite, or may be used in combination with such a porous carrier.

Of course, it may also be used in combination with other ion exchange resins or chelate resins. The resin of the present invention can be used in any form such as beads, powder, lumps, plates, films, rings, threads, etc., but bead-like resins are usually used.

The chelate resin of the present invention exhibits remarkable adsorption ability for heavy metal ions, especially uranium, so it can be used in all uranium-containing solutions.
Particularly advantageously, it can be used to separate and recover uranium from low-concentration uranium solutions, such as from seawater, crude phosphoric acid for fertilizers, uranium mine mine water, uranium smelting wastewater, inbreath leaching solutions, etc. .

When the resin of the present invention is brought into contact with a uranium-containing solution, the iminodi(methylenephosphonic acid) group or the iminomethylenephosphonic acid group forms a very stable chelate with uranium, and the stability constant of the chelate is large, Therefore, it is assumed that uranium is adsorbed with a high adsorption rate and a fast adsorption rate.

Furthermore, the chelate resin of the present invention can also be applied to the selective separation and recovery of useful heavy metal ions other than uranium, such as copper, nickel, zinc, and cobalt. The resin of the present invention can be used in various ways depending on its shape. For example, the resin of the present invention can be packed in a column or tower and a liquid containing uranium or other heavy metals is passed therethrough, or the resin of the present invention can be used as a heavy metal. It is used by immersing it in a solution containing it.

In this case, the temperature of the heavy metal-containing solution is 5°C to 95°C.
The time for contacting the heavy metal ions with the resin is suitably between 1 minute and 50 hours, preferably between 1 minute and 2 hours. In addition, heavy metal ions can be easily recovered from the resin of the present invention that has adsorbed heavy metal ions by contacting them with a mineral acid aqueous solution or an alkaline aqueous solution, in the same way as commercially available chelates, resins, and ion exchange resins, and can be recycled. The resulting resin can be used over and over again. As detailed above, the phenolaldehyde chelate resin of the present invention can be obtained by a simple manufacturing method, and exhibits a special heavy metal trapping effect, particularly an excellent trapping effect for uranium.

Moreover, it is practical because it can be recycled and reused many times with a simple acid treatment, and it is a new resin that can be used for new applications different from conventional phenol alde-based chelate resins. Next, the present invention will be explained in more detail with reference to Examples.

Example 1 1 mole of tyrosine and 2 moles of phosphorous were dissolved in a 20% aqueous solution of hydrochloric acid and heated to reflux while stirring.

In this state, 6 m01 of a 37% formalin aqueous solution was added dropwise over an hour or so, and stirring was continued while refluxing for another hour. Then, after cooling to room temperature, 2 moles of phenol and 4 moles of 37% formalin were added, and the mixture was heated at 90 to 95°C for 30 minutes.
Allowed time to react. After the reaction was completed, the reactant was taken out, pulverized, washed with water, and heated in an air bath at 110 to 120°C for 5 hours to obtain a powdery chelate resin. Example 2 After reacting 1 mole of tyrosine, 2 moles of phosphorous acid, and 6 moles of 37% formalin in the same manner as in Example 1, a 40% NaOH aqueous solution was added to this solution to make it strongly alkaline.

1.5 moles of phenol and 5 moles of formalin were added to this solution and heated at 90° C. for 1 hour, causing the contents to gel.
Take it out, crush it, wash the formalin with water, and
The mixture was heated in an air bath at ~120°C for 5 hours to obtain a powdery chelate resin. Example 3 A mixture of 1 mole of phenol, 1 mole of 37% formalin, and 1 mole of 30% ammonia was added to 40%
The ammonia aresol was formed by heating at 0C for 1 hour.

After adding 2 moles of phosphorous acid and concentrated hydrochloric acid to this liquid to make it strongly acidic, 6 moles of formalin was added in the same manner as in Example 1.
Thereafter, in the same manner as in Example 1, it was crosslinked with 2 moles of phenol and 4 moles of formalin to obtain a powdery chelate resin. Example 4 The resins obtained in Examples 1, 2, and 3 were prepared in advance into 1
000 PPM of uranyl nitrate aqueous solution and 24B! Shake for a while.

Thereafter, the amount of uranyl ions adsorbed on the resin was determined by measuring the concentration of uranyl ions remaining in the liquid. The results are shown in Table 1.

Example 5 Same as Example 2, 1 mole of tyrosine, 2 moles of phosphorous acid, and 3 moles of phosphorous acid.
The mixture was reacted with 6 moles of 7% formalin, and heated soda was further added to make it alkaline.

To this solution, 1.5 mol of resorcin, 5 mol of 37% formalin,
mol was added, and further n-paraffin was added while stirring. Next, while stirring, the mixture was heated at 60°C for 1 hour, 28°C for 1 hour, and 90°C for 1 hour, and the contents began to solidify into particles. Thereafter, the contents were transferred to an autoclave and reacted at 120°C for 5 hours to complete gelation. The resulting granular resin was isolated by filtration, air-dried, washed with water, and then immersed in a 1NH2S04 solution to convert the resin from Na-type to H-type. Thereafter, this resin was separated to obtain bead-shaped chelate resin. Example 6 15 cc of the chelate resin obtained in Example 5 was packed in a column, and 100 PPM (7) UO2 adjusted to PHL with phosphoric acid was added.
A liquid 20f containing 2+ was passed through the tube at a space velocity of 511 hr.

Then after washing? 150 cc of sulfuric acid aqueous solution at a space velocity of 1
The liquid was passed for 11 hours to elute the adsorbed uranium.
The amount of uranium recovered was 85% of the uranium in the phosphoric acid that was passed through. Example 7 1' of seawater (uranium content: 3 μg) was added to 100 m9 of the chelate resin obtained in Example 5, and the mixture was shaken at room temperature for 24 hours.

Claims (1)

[Claims] 1. A compound having a phenolic hydroxyl group and a primary and/or secondary alkylamino group in the same molecule is reacted with phosphorous acid and an aldehyde in the presence of a mineral acid to form the alkylamino group. A phenol having a crosslinked structure characterized by obtaining a reaction product in which some or all of the hydrogen atoms are replaced with methylene phosphonic acid, and then subjecting the obtained reaction product to a condensation reaction with a phenol and an aldehyde. Some of the phenols constituting the aldehyde resin have some or all of the hydrogen atoms directly bonded to the nitrogen atoms of the primary and/or secondary alkylamino groups in the benzene nucleus replaced with methylene phosphonic acid groups. A method for producing phenol/aldehyde chelate resin, which is a phenol. 2. Some of the phenols constituting the phenol-aldehyde resin having a crosslinked structure have a benzene nucleus in which some or all of the hydrogen atoms directly bonded to the nitrogen atoms of the primary and/or secondary alkylamino groups are methylene phosphones. An adsorption treatment method characterized by selectively adsorbing heavy metal ions in an aqueous solution using a phenol/aldehyde chelate resin, which is a phenol substituted with an acid group.